Halogen derivative of the benzanthrone series and process of making same



Patented July 17, 1928.

UNITED STATES 1,677,545 PATENT OLUTO BRAUNSDORF AND EDUARD HOLZAIPFEL, or HOCHST-ON-TKE-MAIN, AND PAUL NAWIASKY, or LUDWIGSHAFEN-ON-THE-BHINE, GERMANY, ASSIGNOBS TO GRAS- v SELLI DYESTUFF oonromrron, or NEW YORK, N. 2., A CORPORATION or DELA- IBLALOGEN' DERIVATIVE OF BENZANTHBONE SERIES AND No Drawing. Application filed March 23, 1926, Serial No. 96,889, and in Germany larch B7, 1925.

y (2) parts of Bzl, Bz1-benzanthronylsulfide, of,the probably formula:

- o v a v The present invention relates to new halogen derivates of sulfur-containing compounds of the benzanthrone'seriesand to a process of preparing the same.

5 We'have found that benzanthronyl mercaptans or benzanthrone disulfides or sulfides or other thio-ethers of benzanthrone-forinstance alkylor aryl-thioether of the general formula vXSY, wherein X repre- 1o sents a benzanthronyl residue (substituted or not), and Y re resents a substituted or unsubstitutedalky aryl; ara1kyl,- or aliphaticacidyl-group, or a hydrogen atom-as they may bekobtained according to U. S. Pat'- ent application Ser. No. 47,966 filed'Augus't 3, 1925, are converted into new'halogenated compounds by treating them with a halogen or an agent splitting oit' halogen. 'The following examples serve to illustrate our invention, all parts being by weight:

(1) 10 parts of Bzl-benzanthronyl mercaptan having the probable formula:

I are introduced, while stirringit into 100 partsof chlorosulfonic' acid at --5 -C. and there are then mine.- When the reaction is complete; the

mass is poured on ice and the --brominate[d t. forms a dark yellow powder'which dissolves product is isolated in the usual manner.-

40 in concentrated sulfuric acid, with a claret red: color, and whenin a dilute solution with a blue color. It probably constitutes a dibromo-Bz1, Bz1-.-benzanthronyldisulfide havving the probable formula :v

stitutes a dichloro-Bzl, Bzl' gradually added 3.1 arts of bro raocnss or m o arestirred in 100 until the evolution. of hydrochloric acid has ceased. "After cooling the product is filtered by suction-Land washed with alcohol. The yellow powder thus obtained probably con- -benzanthr'onylsulfide of the; probable formula OFFICE; 1

i parts of nitrobenaene with 4 lOyparts ofsulfuryl chloride at 75 C.

and is soluble in concentrated sulfuric acid to a violet solutiom I (3) 25 parts of 6,6 diamino-Bzl', B21- bienzanthronylSirlfide-as-it can be produced by causing G-nitro-Bzl-bromobenzanthrone to react with sodium disulfide,are introduced and stirred in 250 parts of nitrobenzene thisv mixture is heated to 50-60" C. and

atthistemperature treated with 25-30 parts of sulfuryl chloride until the, evolution of v. hydrochloric acid has ceased. 'After cool ing the mass is filtered by suction and the'- 7 a0 reaction is freed from the product of the nitrobenzene by washing it with ethyl alco{ hol; It forms let solution. It probably constitutes a dichlorodiamino-henzanthronylsulfide having the probable formula-r I a brown powder which dis solves in concentrated sulfuric acid to a v o- (4) 100 parts of Bzl, Bz1-benzanthronylsulfide are stirred in 1000 parts of chlorosulfonic acid at -5 C. with 17 parts of bromine until all the bromine is consumed. The monobromo-Bzl, Bz1-benzanthronylsulfide, after being isolated in the usual manner, forms an orange-yellow powder which dissolves in concentrated sulfuric acid to abluish-green solution.

(5) If in Example 4 the 17 parts of bromine are replaced by 32parts'of bromine, a dibromo B21, B21 -benzanthronylsulfide is obtained as a yellow powder which dissolves in concentrated sulfuric acid to a green solution. The crude product may be purified by re-crystallization from nitrobenzene.

(6) 10 parts of Bzl, Bzl-benzanthronylsulfide are introduced, while stirring, into 100 parts ,of concentrated sulfuric acid; there are then gradually added 8.5 parts of bromine and the mass is stirred at (SO-70 until the bromine is consumed. After cooling, the mass is poured on ice, the yellowishbrown product which separates is filtered off by suction and washed until neutral. After being dried, it constitutes a yellowish-brown powder-which dissolves in concentrated sulfuric acid to a bluish-green solution. It probably constitutes a tribromo-benzanthronyls'ulfi-de.

(.7) One part of Bzl-benzanthronylthioglycollic acid of the formula:

B-CHa-COOH is introduced into ten times the quantityof bromine and stirred, without any external heating, until there is no further splitting off of hydrogen bromide. The reaction-mixture is then freed from the excess of bromine by means of an indifferent organic solvent.- 'There remains an orange-colored powder ls-oni-coon We claim:

in treating with halogenating agents sulfur compounds of the following eomposihon:

wherein X stands for a benzanthronyl resis" due-which may be substituted or not--and Y stands for a substituted or not-substituted alkylarylor aralkyl group, an aliphatic. acidyl group or a hydrogen atom.

2. Process of producing halogen derivatives of the benzanthronc series consisting in treating with halogenatingagents, in the presence of a diluent, sulfur compounds of the following composition:

wherein X stands for a benzanthronyl residue-which may be substituted or notand Y stands for a substituted or not-substituted alkylarylor aralkyl group, an aliphatic acidyl group or a hydrogen atom.

3. Process of producing halogen derivatives ofthe benzanthrone series, consisting in treating Bzl, Bzl'-benzanthronylsulfide with a halogenating agent.

41. Process of producing halogen derivatives of the benzanthrone series, consisting in treating B21, BZY-benzanthronylsulfide with a halogenating agent in the presence of a diluent.

5. As new products, halogenated sulfur compounds of the benzanthrone series of the following formula halogenated 1113 wherein X stands for a benzanthronyl residue-.which may be substituted or not- -and Y stands for a substituted or not-substituted alkylaryl or aralkyl group, an aliphatic acidyl group or a hydrogen atom.

6. As a new product, monobromo-Bzl, Bzl'-benzanthronylsulfide, being a yellow powder, soluble in concentrated sulfuric acid to a bluish-green solution.

7. As new products, halogenated sulfur compounds of the benzanthrone series having the type formula:

wherein Hlg represents halogen and n representsa whole number not greater than 3.

In testimony whereof, we afiix our signaoTTo BRAUNSDORF. EDUARD HOLZAPFEL. PAUL NAWIASKY.

' tures. 

